A High Capacity Calcium Primary Cell Based on the Ca–S System

Conversion reaction cells afford the ability to explore new energy storage paradigms that transcend the dogma of small, low‐charge cations essential to intercalative processes. Here we report the use of earth‐abundant and green calcium and sulfur in unprecedented conversion reaction Ca–S primary cells. Using S‐infiltrated mesoporous carbon (abbreviated S@meso‐C) cathodes, we achieve discharge capacities as high as 600 mAh g^(−1) (S basis) within the geometry Ca|Ca(ClO_4)_2/CH_3CN|S@meso‐C, at a discharge rate of C/3.5. The electrolyte system in the Ca–S battery is of paramount importance as the solid electrolyte interface (SEI) formed on the Ca anode limits the capacity and stability of the cell. We determine that 0.5 M Ca(ClO_4)_2 in CH_3CN forms an SEI that advantageously breaks down under anodic bias to allow oxidation of the anode. This same SEI, however, exhibits high impedance which increases over time at open circuit limiting the shelf life of the cell

A High Capacity Calcium Primary Cell Based on the Ca–S System

Conversion reaction cells afford the ability to explore new energy storage paradigms that transcend the dogma of small, low‐charge cations essential to intercalative processes. Here we report the use of earth‐abundant and green calcium and sulfur in unprecedented conversion reaction Ca–S primary cells. Using S‐infiltrated mesoporous carbon (abbreviated S@meso‐C) cathodes, we achieve discharge capacities as high as 600 mAh g^(−1) (S basis) within the geometry Ca|Ca(ClO_4)_2/CH_3CN|S@meso‐C, at a discharge rate of C/3.5. The electrolyte system in the Ca–S battery is of paramount importance as the solid electrolyte interface (SEI) formed on the Ca anode limits the capacity and stability of the cell. We determine that 0.5 M Ca(ClO_4)_2 in CH_3CN forms an SEI that advantageously breaks down under anodic bias to allow oxidation of the anode. This same SEI, however, exhibits high impedance which increases over time at open circuit limiting the shelf life of the cell

Bimodal Mesoporous Titanium Nitride/Carbon Microfibers as Efficient and Stable Electrocatalysts for Li–O_2 Batteries

The rechargeable Li–O_2 battery has been considered as a sustainable chemical power source for electric vehicles and grid energy storage systems due to the high theoretical specific energy (∼3500 Wh/kg). The practical performance of Li–O_2 batteries is, however, still far below expectations. This is mainly attributed to the (1) intrinsic sluggish reaction kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), (2) passivation of the electrodes by electrical isolation and pore blocking, and (3) chemical instability of the organic cell components, i.e., electrolyte, polymer binder, and carbon electrode, in the presence of O_2•– and Li_2O_2. It is crucial to develop highly porous, three-dimensional, conducting cathode catalyst/gas diffusion layer (GDL) architectures possessing superior catalytic activity and stability with respect to the ORR and the OER in order to address these issues. All of these requirements prompted us to examine the catalytic performance of porous framework metal nitride electrodes for Li–O_2 batteries

Sulfur-Functionalized Mesoporous Carbons as Sulfur Hosts in Li–S Batteries: Increasing the Affinity of Polysulfide Intermediates to Enhance Performance

The Li–S system offers a tantalizing battery for electric vehicles and renewable energy storage due to its high theoretical capacity of 1675 mAh g^(–1) and its employment of abundant and available materials. One major challenge in this system stems from the formation of soluble polysulfides during the reduction of S_8, the active cathode material, during discharge. The ability to deploy this system hinges on the ability to control the behavior of these polysulfides by containing them in the cathode and allowing for further redox. Here, we exploit the high surface areas and good electrical conductivity of mesoporous carbons (MC) to achieve high sulfur utilization while functionalizing the MC with sulfur (S–MC) in order to modify the surface chemistry and attract polysulfides to the carbon material. S–MC materials show enhanced capacity and cyclability trending as a function of sulfur functionality, specifically a 50% enhancement in discharge capacity is observed at high cycles (60–100 cycles). Impedance spectroscopy suggests that the S-MC materials exhibit a lower charge-transfer resistance compared with MC materials which allows for more efficient electrochemistry with species in solution at the cathode. Isothermal titration calorimetry shows that the change in surface chemistry from unfunctionalized to S-functionalized carbons results in an increased affinity of the polysulfide intermediates for the S–MC materials, which is the likely cause for enhanced cyclability

Sulfur infiltrated mesoporous graphene–silica composite as a polysulfide retaining cathode material for lithium–sulfur batteries

The lithium–sulfur (Li–S) system is an attractive candidate to replace the current state-of-the-art lithium-ion battery due to the promising theoretical charge capacity of 1675 mA h/g and energy density of 2500 Wh/kg; however, the dissolution of intermediate polysulfides into the organic liquid electrolyte during cycling hinders its practical realization. We report the synthesis of mesoporous graphene–silica composite (m-GS) as a supporting material of sulfur for Li–S batteries. The ordered porous silica structure was synthesized parallel to functionalized graphene sheets (FGSs) through the ternary cooperative assembly of the graphene, silica, and block copolymer precursors. The well-defined, unique mesoporous structure integrates the electronic conductivity of graphene and the dual functions of silica as a structure building block and in situ polysulfide ab-/ad-sorbing agent to give a Li–S battery that has both good retention ability of polysulfides and good rate capability

A manutenção preventiva das edificações: o olhar dos gestores

Dissertação (mestrado profissional) - Universidade Federal de Santa Catarina, Centro Sócio-Econômico, Programa de Pós-Graduação em Administração Universitária, Florianópolis, 2017.A presente Dissertação foi desenvolvida com o objetivo de compreender como os gestores do Instituto Federal de Educação, Ciência e Tecnologia de Santa Catarina (FSC) concebem, diante da Política Pública de Expansão da Rede Federal de Educação Profissional e Tecnológica (BRASIL, 2005), a Política Institucional de Manutenção Preventiva das Edificações. Foi elaborada com base em um estudo de caso, de natureza qualitativa, por meio de entrevistas semiestruturadas. Os resultados da pesquisa apontam a Política Institucional de Manutenção Preventiva das Edificações como a ferramenta necessária para a preservação do patrimônio imobiliário do IFSC, bem como a para a manutenção do processo histórico e cultural vivenciado pela Instituição. Os gestores reconhecem a importância da Política Pública de Expansão (BRASIL, 2005) no desenvolvimento do Departamento de Obras e Engenharia, assim como a importância deste para a expansão da Instituição. Na visão dos sujeitos da pesquisa, o IFSC não possui um Política Institucional de Manutenção Preventiva formalizada, mas possui uma prática de manutenção, a qual é de responsabilidade do Departamento de Obras e Engenharia. A Política Pública de Expansão (BRASIL, 2005) apesar de grande relevância para a Educação Nacional, na concepção dos gestores, trouxe desafios para com a manutenção do patrimônio imobiliário proveniente desta. Contudo, no desenvolvimento deste Estudo, uma contradição se evidenciou, ao mesmo tempo que a manutenção preventiva das edificações é uma prática da gestão, esta é negada, pela falta de uma concepção de gestão, de uma Política Institucional de Manutenção Preventiva das Edificações. Com vistas a tentar superar esta contradição, destacam-se ações que fomentem a capacitação dos gestores sobre a importância da manutenção preventiva das edificações e a priorização do desenvolvimento de diretrizes para uma Política Institucional de Manutenção Preventiva das Edificações do IFSC.Abstract : The present research aims at undertanding how the managers of the Instituto Federal de Ciência e Tecnologia de Santa Catarina (IFSC) conceive the Institucional Policy of Preventive Maintenance of Buildings, before the Public Expansion Policy of Federal Network of Professional and Technological Education (BRASIL, 2005). It was elaborated based on a qualitative case study, by means of a semi-estructured interviews. The results of research indicate the Institutional Policy of Preventive Maintenance of Buildings like a required tool to preserve the real estate heritage of IFSC as, it is important for the preservation of historic and cultural process experienced by the Institution. The managers recognize the importance of Public Expansion Policy (BRASIL, 2005) in the developement of Building and Engineering Department of IFSC as well as, the importance of this Department for the institutional expansion. In the view of the research participants, IFSC has not formalized an institutional policy of preventive maintenance of the buildings. On the other hand, it has a maintenance practice, which is the responsability of Building and Engineering Department. The Public Expansion Policy (BRASIL, 2005) is relevant to the National Education according to the managers conception but, it brounght some dare to the maintenance of the real estate heritage originated from this expansion. However, the development of this study disclosed a contradiction, at the same time the preventive maintenance of buildings is a management practice, it is denied by the lack of a management conception of an institutional policy of preventive maintenance of buildings. In order to overcome this contradiction, some evident actions are highlignted, which promote a training to teach the comunity and managers about the importance of preventive maintenance of buildings and actions that prioritize the development of guidelines for an institutional policy of preventive maintenance of buildings of IFSC

Bimodal Mesoporous Titanium Nitride/Carbon Microfibers as Efficient and Stable Electrocatalysts for Li–O_2 Batteries

The rechargeable Li–O_2 battery has been considered as a sustainable chemical power source for electric vehicles and grid energy storage systems due to the high theoretical specific energy (∼3500 Wh/kg). The practical performance of Li–O_2 batteries is, however, still far below expectations. This is mainly attributed to the (1) intrinsic sluggish reaction kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), (2) passivation of the electrodes by electrical isolation and pore blocking, and (3) chemical instability of the organic cell components, i.e., electrolyte, polymer binder, and carbon electrode, in the presence of O_2•– and Li_2O_2. It is crucial to develop highly porous, three-dimensional, conducting cathode catalyst/gas diffusion layer (GDL) architectures possessing superior catalytic activity and stability with respect to the ORR and the OER in order to address these issues. All of these requirements prompted us to examine the catalytic performance of porous framework metal nitride electrodes for Li–O_2 batteries

Nanoscale surface compositions and structures influence boron adsorption properties of anion exchange resins

International audienceBoron adsorption properties of poly(styrene-co-divinylbenzene) (PSDVB)-based anion-exchange resins with surface-grafted N-methyl-d-glucamine (NMDG) depend strongly on their local surface compositions, structures, and interfacial interactions. Distinct boron adsorption sites have been identified and quantified, and interactions between borate anions and hydroxyl groups of NMDG surface moieties have been established. A combination of X-ray photoelectron spectroscopy (XPS), solid-state nuclear magnetic resonance (NMR), and Fourier-transform infrared (FT-IR) spectroscopy were used to characterize the atomic-level compositions and structures that directly influence the adsorption of borate anions on the NMDG-functionalized resin surface. Surface-enhanced dynamic-nuclear-polarization (DNP)-NMR enabled dilute (3 atom % N) tertiary alkyl amines and quaternary ammonium ions of the NMDG groups to be detected and distinguished with unprecedented sensitivity and resolution at natural abundance 15N (0.4%). Two-dimensional (2D) solid-state 11B{1H}, 13C{1H}, and 11B{11B} NMR analyses provide direct atomic-scale evidence for interactions of borate anions with the NMDG moieties on the resin surfaces, which form stable mono- and bischelate complexes. FT-IR spectra reveal displacements in the stretching vibrational frequencies associated with the O-H and N-H bonds of NMDG groups that corroborate the formation of chelate complexes on the resin surfaces. The atomic-level compositions and structures are related to boron adsorption properties of resin materials synthesized under different conditions, which have important remediation applications

Synthesis of amorphous silicon carbide nanoparticles in a low temperature low pressure plasma reactor

Commercial scale production of silicon carbide (SiC) nanoparticles smaller than 10 nm remains a significant challenge. In this paper, a microwave plasma reactor and appropriate reaction conditions have been developed for the synthesis of amorphous SiC nanoparticles. This continuous gas phase process is amenable to large scale production use and utilizes the decomposition of tetramethylsilane (TMS) for both the silicon and the carbon source. The influence of synthesis parameters on the product characteristics was investigated. The as-prepared SiC particles with sizes between 4 and 6 nm were obtained from the TMS precursor in a plasma operated at low temperature and low precursor partial pressure (0.001-0.02 Torr) using argon as the carrier gas (3 Torr). The carbon:silicon ratio was tuned by the addition of hydrogen and characterized by x-ray photoelectron spectroscopy. The reaction mechanism of SiC nanoparticle formation in the microwave plasma was investigated by mass spectroscopy of the gaseous products